Method and apparatus for detecting hydrocarbon fuel leaks

ABSTRACT

A method of and apparatus for detecting fuel leaks employing color variable indicators are disclosed. The method comprises the steps of preparing and applying a water soluble non-staining indicator dye to a test surface, observing color changes indicative of hydrocarbon leaks and removing the indicator dye from the test surface. The apparatus comprises in combination an apparatus for preparing the indicator dye, a spray apparatus for applying the indicator dye to the test surface and surface cleaning apparatus for removing the dye from the test surface. The indicator dye comprises a major portion of a dry inert mineral carrier and from about 0.1 to about 5.0 weight percent of a direct dye which is non-staining on painted surfaces and which does not migrate into or penetrate polyurethane or epoxy resin base painted surfaces.

This is a division of co-pending application Ser. No. 607,450, filed on May 7, 1984.

TECHNICAL FIELD

This invention relates to an improved leak indicator and a method of using the same to detect fuel leaks in aircraft. More particularly, it relates to an improved leak indicator which is easily removed from surfaces being tested and which does not stain the painted surfaces being tested.

BACKGROUND ART

Leak detection is an essential aspect of quality control in the construction of aircraft fuel tanks and the like. To check the integrity of tanks during and after construction a variety of methods are used, for example, the tank is pressurized with air and a soap film is applied to the area being inspected and the formation of bubbles is visually noted. Another method involves pressurizing the tank being tested with ammonia gas and spraying the surface being tested with a viscous liquid which contains an acid-base indicator which will change color if a tank leak allows ammonia gas to escape. Still another method of testing for leaks involves pressurizing the tank with helium gas and detecting escaping gas with a mass spectrometer. Yet another method for detecting leaks in fuel tanks uses thermographic techniques. Another method of detecting fuel leaks in both partially assembled or assembled aircraft involves applying an oil red 0 dyed talc to the surface being tested. The talc is applied by mixing it with 1,1,1 trichloroethane and spraying the mixture onto the surface being tested. The trichloroethane quickly evaporates leaving a pink powder on the test area. This method has been found to be an effective indicator of fuel tank leaks, however, the material used in the test procedure has several undesirable characteristics. The dye oil red 0 is a petroleum dye that is soluble in hydrocarbon solvents such as 1,1,1 trichloroethane and JP-5 jet fuel and this solubility causes some of the dye to migrate from the talc carrier into the surface of the paint used on the test area thereby staining it. Another undesirable characteristic is the similarity of the relation of the oil red 0 dye with water and its reaction to jet fuel. If either fuel or water contacts the oil red 0 impregnated talc the color of the talc changes from pink to red thus making the test meaningless if water is present as a mist, spray, or as falling rain. This characteristic of the dye decreases the usefulness of the test in the field. Other methods of detecting leaks are disclosed in U.S. Pat. Nos. 3,368,994; 3,287,156; and 3,266,920.

DISCLOSURE OF THE INVENTION

Accordingly, it is an object of the present invention to provide a leak detection method which is applicable to any container of hydrocarbon fuel.

Another object of the present invention is to provide a leak detection method which will not color or stain the surface being tested.

It is another object of the present invention to provide a dry indicator material capable of detecting hydrocarbon fuels without coloring or staining the surface being tested.

Yet another object of the present invention is to provide an indicator material which is capable of distinguishing between water and hydrocarbon fuels.

Yet another object of the present invention is to provide a method of detecting hydrocarbon fuel leaks which will not damage the surface being tested.

Still another object of the present invention is to provide a method of producing an indicator material suitable for detecting hydrocarbon fuel leaks without staining the surface being tested.

A further object of the present invention is to provide a method of applying a dry test material to a surface without damage to the surface being tested.

Still a further object of the present invention is to provide a method of removing an indicator from a test surface without staining or otherwise damaging the test surface.

These and other objects, features and advantages of the present invention are accomplished by providing a method of and apparatus for detecting hydrocarbon fuel leaks in a vessel, tank or container for the same which comprise a new indicator powder consisting of a direct dye in combination with inert mineral carrier. The direct dye used is soluble in water and lower chain alcohols and insoluble in hydrocarbon fuels. The dye is non-staining on painted surfaces and does not migrate into or penetrate painted surfaces containing a polyurethane or epoxy resin base. The method of preparing the new indicator powder of the present invention comprises the steps of preparing a solution of the direct dye and mixing the direct dye solution with sufficient inert mineral carrier to form a thick slurry, drying the slurry to form a dyed carrier and milling the dyed carrier to form a dyed powder having an even color and uniform particle size distribution. The dyed powder or indicator powder is subsequently used to detect hydrocarbon leaks by introducing fuel into a fuel tank and allowing the fuel to soak the container for a time, applying the indicator powder to the surface being tested, observing any color changes that might take place and removing the indicator powder from the surface being tested.

The principal feature of the present invention is the provision of method and means for the detection of leaks in assembled and mounted fuel tanks without staining or otherwise damaging painted test surfaces.

Another important feature of the present invention is the provision of a composition of matter suitable for detecting hydrocarbon liquids by color change which is non-staining on painted surfaces and which does not migrate into or penetrate painted surfaces coated with a paint containing a polyurethane or epoxy resin base.

Yet another important feature of the present invention is the provision of a method of manufacturing a composition of matter suitable for detecting hydrocarbon liquids by color change which is non-staining on painted surfaces.

Still another important feature of the present invention is the ability of the indicator powder to be removed from a test surface merely by flushing the surface with water.

Another important feature of the present invention is the ability of the indicator powder to be removed from a test surface merely by brushing.

A further feature of the present invention is the provision of a portable aerosol container of the detecting powder which can be used in areas not equipped with large spray apparatus. Thus the ability to locate the fuel tank leaks under field conditions is substantially improved.

One advantage of the present invention is that the present leak detection method complements other leak detection methods such as thermographic methods which are used principally on unassembled sections and tanks.

Another advantage of the present leak detecting method is the non-staining nature of the dye used to produce the indicator powder in that costly and time consuming cleanup after testing is eliminated.

Another advantage of the present method is that a tank can be leak tested without exposing test personnel to noxious, irritating and toxic gases.

In accordance with the present invention the method of detecting hydrocarbon leaks further comprises the step of combining the dyed carrier with an organic solvent to form an indicator suspension and spraying the indicator suspension onto the surface. The organic solvent used to prepare the suspension must be sufficiently volatile to volatilize during spraying thereby allowing for the deposition of a dry, finely-divided indicator powder onto the surface being tested.

The method of detecting hydrocarbon fuel leaks further comprises spraying the indicator suspension onto the surface being tested at pressure less than or equal to 45 psi above the ambient pressure.

The present invention also comprises the composition of matter for detecting leaks in aircraft fuel tanks comprising a major portion of a dry mineral carrier selected from a group consisting of diatomaceous earth, kaolin clay, talc, fumed silica, silicondioxide and mixtures thereof and from about 0.1 to about 5.0 weight percent of a water soluble salt of a sulfonic acid of an azo dye selected from a group consisting of:

7-hydroxy-8-(4-phenylazophenylazo)-1,3-naphthalindesulfonic acid disodium salt;

4,6-dihydroxy-3[4-[1-[4-[[1-hydroxy-7-[(phenysulfonyl)oxy]-3-sulfo-2-naphthalenyl]azo]phenyl]cyclohexyl]phenyl]azo]-2-naphthalenesulfonic acid disodium salt;

N-[4-[[4-(diethylamino)phenyl][4-[ethyl[3-sulfophenyl)methyl]amino]phenyl]methylene]-2,5-cyclohexadien-1-yliden]-N-ethyl-3-ethyl-3-sulfohydroxide-, benzenemethanaminium inner salt disodium salt;

5-(acetylamino)-4-hydroxy-3-(phenylazo)-2,7-naphthalenedissulfonic acid disodium salt;

2,2'-[9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl-benzenesulfonic acid disodium salt]

7-hydroxy-8-(phenylazo)-1,3-naphthalenedisulfonic acid disodium salt;

4-hydroxy-3-[[4-methyl-3-[phenylamino)sulfonyl]phenyl]azo]-1-naphthalenesulfonic acid monosodium salt;

5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalenedisulfonic acid disodium salt;

N-ethyl-N-[4-[[4-[ethyl[(3 sulfophenyl)methyl]amino]cyclohexadien-1-ylidene]-3-sulfo-hydroxide benzenemethanominium inner salt sodium salt;

2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracendiyl)diimino]bis[5 butyl-, benzenesulfonic acid]disodium salt;

2,2'-[9,10-dihydro-5,8-dihydroxy-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl-benzenesulfonic acid]disodium salt;

4-[(2-hydroxy-1-naphthalenyl)azo]-benzenesulfonic acid monosodium salt;

5-(acetylamino)-3-[[4-(acetylamino)phenyl)azo]-4-hydroxy-2,7-naphthalenedisulfonic acid]disodium salt;

4-[(2-hydroxy-1-naphthalenyl)azo]-1-naphthalenesulfonic aicd monosodium salt;

5-[(2-hydroxy-1-naphthalenyl)azo]-1-naphthalenesulfonic acid monosodium salt;

5-(acetylamino)-4-hydroxy-3-phenylazo-2,7-naphthalenedisulfonic acid disodium salt;

4-hydroxy-3-[(4-sulfo-1-naphthalenyl)azo]-1-naphthalenesulfonic acid disodium salt;

3,3'-[cyclohexylidenebis[(2-methyl-4,1-phenylene)azo]]bis[4,6-dihydroxy-4-naphthalenesulfonic acid disodium salt;

7-hydroxy-8-[[4-(phenylazo)phenyl]azo]-1,3-naphthalenedisulfonic acid disodium salt;

4-[(2,4-dimethylphenyl)azo]-3-hydroxy-2,7-naphthalenedisulfonic acid disodium salt;

7-hydroxy-8-[(4-sulfo-1-naphthalenyl)azo]-1,3-naphthalenedisulfonic acid tridosium salt;

N-[-4[[4-dimethylamino)phenyl][4-[ethyl[3-sulfophenyl)methyl]amino]phenyl]mithylene]-2,5-cyclohexadien-1-yliden]-N-ethyl-3-sulfo,benzenemethanaminium hydroxide inner salt sodium salt;

N-[-[[4-(dimethylamino)phenyl][2-ethoxy-4-[(4-methylsulfophenyl)amino]-2-sulfophenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-methylhydroxide methanaminium inner salt monosodium salt;

7-hydroxy-8-(1-naphthalenylazo)-1,3 naphthalendisulfonic acid disodium salt;

N-[4-[[4-diethylamino)phenyl]phenylmethylene]-2,5-cyclohexadien-1-ylidene]-N-ethyl-ethanaminium sulfate;

4-hydroxy-5-[[(4-methylphenyl)sulfonyl]amino]-3-(phenylazo)-2,7,naphthalenedisulfonic acid disodium salt;

4-amino-3-[(2,5-dichlorophenyl)azo]-5-hydroxy-6-[[4'-[(4-hydroxyphenyl)azo][1,1'-biphenyl]-4-yl]azo]2,7-naphthalenedisulfonic acid disodium salt;

7,7'-(carbonyldiimino)bis[4-hydroxy-3-(phenylazo)-2-naphthalenesulfonic acid disodium salt;

3-[[4-[[6-[(4-aminobenzoyl)amino]-1-hydroxy-3-sulfo-2-naphthalenyl]azo]-3,5-dimethylphenyl]azo]-1,5-naphthalenesulfonic acid tri sodium salt;

5-[[4'-[(2-amino-8-hydroxy-6-sulfo-1-naphthalenyl)azo][1,1]-biphenyl]-4-yl]azo]-2-hydroxy-benzoic acid disodium salt;

3-[[4-(acetylamino)phenyl]azo]-4-hydroxy-7-[[[[5-hydroxy-6-(phenylazo)-7-sulfo-2 naphthalenyl]amino]carbonyl]amino]-2 naphthalenesulfonic acid disodium salt;

4-amino-5-hydroxy-6-[[4'-[(4-hydroxyphenyl)azo][1,1'-biphenyl]-4-yl]azo]-3-[(4-nithophenyl)azo]2,7-naphthalene disulfonic acid disodium salt;

4-amino-5-hydroxy-3-[[4'-[(4-hydroxy phenyl)azo][1,1'biphenyl]-4-yl]azo]-6-(phenylazo)-2,7-naphthalenedisulfonic acid disodium salt;

5-[[4'-[[8-amino-1-hydroxy-7-[(4-nitrophenyl)azo]-3,6-disulfo-2-naphthalenyl]azo[[1,1'-biphenyl]-4-yl]azo]-2-hydroxy-benzoic aicd trisodium salt;

2,-]2-(4-nitro-2-sulophenyl)ethenyl]-5-[[4-[(4-sulfophenyl)azo]phenyl]-NNO-azoxy]-benzenesulfonic acid trisodium salt;

5,5'[carbonylbis[imino(2-sulfo-4,1-phenylene)azo][[bis[6-amino-V-hydroxy-2-naphthalenesulfonic]acid tetrasodium salt;

4,4'-[carbonylbis[imino(5-methoxy-2-methyl-4,1-phenylene)azo]]bis[5-hydroxy-2,7-naphthalenedisulfonicacid]tetrasodium salt;

7-(benzoylamino)-4-hydroxy-3-[[4-[(4-sulfophenyl)azo]phenyl]azo]-2-naphthalenesulfonic acid disodium salt;

[-[[5,5'-[carbonylyl bis[imino(2-hydroxy-5 sulfo-4,1-phenylene)azo]]bis[6-hydroxy-2-naphthalenesulfonate]]ditetroammonium cuprate

[-[[7,7'-(carbonyldiimino)bis[4 hydroxy-3-[(2-hydroxy-5-sulfophenyl)azo]-2-naphthalenesulfonato](8-)]]dicuprate tetrasodium;

[-[[7,7'-iminobis[4-hydroxy-3-[[2-hydroxy-5-[(methylamino)sulfonyl]phenyl]azo]-2-naphthalenesulfonato]](6-)]]dicuprate disodium;

7-(benzoylamino)-4-hydroxy-3-[[2-methoxy-5-methyl-4-[(4-sulfophenyl)azo]phenyl]azo]-2-naphthalenesulfonic acid disodium salt;

5-[[4'[(26-diamino-3-methyl-5-sulfophenyl)azo]-3,3'-dimethyl[1,1'-biphenyl]-4-yl]azo]-2-hydroxy-benzoic acid disodium salt;

7,7'-iminobis[4-hydroxy-3-(phenylazo)-2-naphthalenesulfonic acid disodium salt;

3-3'-[3,3'-dimethyl[1,1'-biphenyl]-4,4'diyl)bis(azo)]bis[4-amino-5-hydro y-1,-naphthalensulfonic acid disodium salt;

7,7'-iminobis[4-hydroxy-3-(phenylazo)-1-naphthelenesulfonic acid disodium salt;

5-[[4'-[2-amino-8-hydroxy-6-sulfo-1-naphthalenyl)azo][1,1'biphenyl)-4-yl]azo]-2-hydroxy-benzoic acid

5,5'[carbonylbis[imino(1-hydroxy-3-sulfo-6,2-naphthalenediyl)azo][bis-1 naphthalenesulfonic acid tetrasodium salt;

7,7'iminobis[4-hydroxy-3-(phenylazo)-2-naphthaolenesulfonic acid disodium salt;

3-[[4-(acetylamino)phenyl]azo]-4-hydroxy-7-[[[5-hydroxy-6-(phenylazo)-7-sulfo-2-naphthalenyl]amino]carbonyl]amino]-2-naphthalenesulfonic acid;

8-[[4'-[4-ethoxyphenyl)azo][1,1'-biphenyl]-4-yl]azo]-7-hydroxy-1,3-naphthalenedisulfonic acid disodium salt;

3-[[4-(acetylamino)phenyl]azo]-4-hydroxy-7-[[[[5-hydroxy-6-)phenylazo)-7-sulfo-2-naphthalenyl]amino]carbonyl]amino]-2-naphthalenesulfonic acid disodium salt;

5,5'[[1,1'biphenyl]-4,4'-diylbis(azo)]bis[6-amino-4-hydroxy-2-naphtholene sulfonic acid disodium salt;

7-amino-3-[[4'[(2-amino-8-hydroxy-6-sulfo-1-naphthalenyl)azo][1,1'-biphenyl]-4-yl]azo]-4-hydroxy-2-naphthalene sulfonic acid disodium salt;

5-[[4-[[1-hydroxy-6-(phenylamino)-3-sulfo-2-naphthalenyl]azo]-5-methoxy-2-methylphenyl]azo]-1-naphtholenesulfonic acid disodium salt.

The composition of matter of the present invention also comprises lower chain alcohol soluble salts of sulfonic acids of azo dyes which are essentially non-staining on painted surfaces and which will not migrate into or penetrate painted surfaces containing a polyurethane or epoxy resin base.

The composition of matter of the present invention also comprises a direct dye absorbed onto the surface of inert mineral carrier partices having a diameter of less than microns.

Ideally the composition of matter of the present invention comprises a direct dye absorbed onto the surface of inert mineral carrier particles having a diameter greater than 1 micron and less than 10 microns.

Further, in accordance with the present invention the indicator slurry is dried at a temperature of from about 100° C. to about 250° C. for sufficient time to drive off substantially all solvent from the slurry, generally from about one to about eight hours thereby forming an indicator cake.

Also, in accordance with the present invention, the indicator cake is milled to produce an indicator powder having an even color and uniform particle size. One method of milling the indicator cake is using a jar mill with a charging ratio of about 40 percent by volume grinding media and about 25 percent by volume indicator cake. Ideally the milling step is combined with the drying step.

Also in accordance with the present invention the indicator is applied to the surface being tested as an aerosol spray and in this application the suspension will include from about 0.1 to about 1.0 weight percent of a suspending agent such as aluminum stearate, calcium stearate, magnesium stearate and stearic acid and may be contained in a device equipped with a mixing means or agitator to prevent hard settling of the suspended indicator.

These and other objects, features and advantages of the present invention will be more apparent from the the following more detailed description of the preferred embodiments as illustrated in the accompanying drawings. The drawings are not necessarily to scale, emphasis instead being placed on illustrating the principles of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram illustrating the steps of a method of a preferred embodiment of the invention.

FIG. 2 is a block diagram illustrating the steps of a method of a preferred embodiment of the invention.

FIG. 3 schematically illustrates an apparatus for detecting leaks in a fuel tank in accordance with the present invention.

FIG. 4 illustrates one embodiment of a means for applying the indicator suspension of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

A general schematic illustration of a preferred method for manufacturing indicator powder appears in FIG. 1. A suitable dye and solvent are mixed to form a dye solution. For example, a dye solution containing 1.0 percent by weight of 7-hydroxy-8-(4-phenylazophenylazo)-1,3-naphthalindedisulfonic acid disodium salt (croceine M00 dye) is prepared using water as the solvent. In this particular instance the dye solution prepared in mixing step 10 produces a red color when the concentration of the croceine dye equals or exceeds 0.8 weight percent. The maintenance of a red color is preferable because the color change resulting when hydrocarbon fuels contact the indicator powder is easier to see thereby reducing the possibility that a leak will not be detected because the color change was difficult to see. The dye solution is mixed with a mineral carrier such as diatomaceous earth, kaolin, talc, fumed silica, silicon dioxide or a mixture of such inert mineral carriers. If diatomaceous earth is used the dye solution is mixed with the mineral carrier in a ratio of about 1.6 parts to 1 part, respectively, to form a dark red clay-like material. Good results have also been obtained mixing about 1.8 parts dye solution with about 1.0 parts diatomaceous earth. When mixed together the dye solution and the croceine dye form a slurry-like material having a dark red color. The slurry is dried in a static dryer to form a solid cake-like mass 13B for later milling into a powder to dried in a combination dryer and mill so that all the time drying is occurring the dye coated mineral is being ground into powder 13A. Care must be taken to prevent over-milling the carrier or the absorbant structure of the mineral particles will be destroyed. One method of milling is a jar mill in which 40 percent by volume of the mill charge is grinding media and 25 percent by volume of the mill charge is the indcator being ground into a powder having an average particle size less than 10 microns. Once grinding is complete, the indicator powder is ready for use in detecting hydrocarbon fuel leaks or packaging for storage and subsequent use.

The indicator powder produced by this process generally consists of a major portion, from about 99.9 weight percent to about 95.0 weight percent of a dry inert mineral carrier and from about 0.1 to about 5.0 weight percent of a dye which is soluble in water and lower chain alcohols. The dye is also essentially non-staining on painted surfaces and does not migrate into or penetrate painted surfaces which contain a polyurethane or an epoxy resin base. Among the dyes suitable for use in the indicator powder are:

7-hydroxy-8-(4-phenylazophenylazo)-1,3-naphthalindesulfonic acid disodium salt;

4,6-dihydroxy-3[4-[1-[4-[[1-hydroxy-7-[(phenysulfonyl)oxy]-3-sulfo-2-naphthalenyl]azo]phenyl]cyclohexyl]phenyl]azo]-2-naphthalenesulfonic acid disodium salt;

N-[4-[[4-(diethylamino)phenyl][4-[ethyl[3-sulfophenyl)methyl]amino]phenyl]methylene]-2,5-cyclohexadien-1-yliden]-N-ethyl-3-ethyl-3-sulfohydroxide-, benzenemethanaminium inner salt disodium salt;

5-(acetylamino)-4-hydroxy-3-(phenylazo)-2,7-naphthalenedissulfonic acid disodium salt;

2,2'-[9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl-benzenesulfonic acid disodium salt]

7-hydroxy-8-(phenylazo)-1,3-naphthalenedisulfonic acid disodium salt;

4-hydroxy-3-[[4-methyl-3-[phenylamino)sulfonyl]phenyl]azo]-1-naphthalenesulfonic acid monosodium salt;

5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalenedisulfonic acid disodium salt;

N-ethyl-N-[4-[[4-[ethyl[(3 sulfophenyl)methyl]amino]cyclohexadien-1-ylidene]-3-sulfo-hydroxide benzenemethanominium inner salt sodium salt;

2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracendiyl)diimino]bis(5 butyl-,benzenesulfonic acid]disodium salt;

2,2'-[9,10-dihydro-5,8-dihydroxy-9,10-dioxo-1,4-anthracenediyl)diimino]bis[5-methyl-benzenesulfonic acid]disodium salt;

4-[(2-hydroxy-1-naphthalenyl)azo]-benzenesulfonic acid monosodium salt;

5-(acetylamino)-3-[[4-(acetylamino)phenyl)azo]-4-hydroxy-2,7-naphthalenedisulfonic acid]disodium salt;

4-[(2-hydroxy-1-naphthalenyl)azo]-1-naphthalenesulfonic aicd monosodium salt;

5-[(2-hydroxy-1-naphthalenyl)azo]-1-naphthalenesulfonic acid monosodium salt;

5-(acetylamino)-4-hydroxy-3-phenylazo-2,7-naphthalenedisulfonic acid disodium salt;

4-hydroxy-3-[(4-sulfo-1-naphthalenyl)azo]-1-naphthalenesulfonic acid disodium salt;

3,3'-[cyclohexylidenebis[(2-methyl-4,1-phenylene)azo]]bis[4,6-dihydroxy-4-naphthalenesulfonic acid disodium salt;

7-hydroxy-8-[[4-(phenylazo)phenyl]azo]-1,3-naphthalenedisulfonic acid disodium salt;

4-[(2,4-dimethylphenyl)azo]-3-hydroxy-2,7-naphthalenedisulfonic acid disodium salt;

7-hydroxy-8-[(4-sulfo-1-naphthalenyl)azo]-1,3,-naphthalenedisulfonic acid tridosium salt;

N-[-4[[4-dimethylamino)phenyl][4-[ethyl[3-sulfophenyl)methyl]amino]phenyl]mithylene]-2,5-cyclohexadien-1-yliden]-N-ethyl-3-sulfo,benzenemethanaminium hydroxide inner salt sodium salt;

N-[-[[4-(dimethylamino)phenyl][2-ethoxy-4-[(4-methylsulfophenyl)amino]-2-sulfophenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-methylhydroxide methanaminium inner salt monosodium salt;

7-hydroxy-8-(1-naphthalenylazo)-1,3 naphthalendisulfonic acid disodium salt;

N-[4-[[4-diethylamino)phenyl]phenylmethylene]-2,5-cyclohexadien-1-ylidene]-N-ethyl-ethanaminium sulfate;

4-hydroxy-5-[[(4-methylphenyl)sulfonyl]amino]-3-(phenylazo)-2-7,naphthalenedisulfonic acid disodium salt;

4-amino-3-[(2,5-dichlorophenyl)azo]-5-hydroxy-6-[[4'-[(4-hydroxyphenyl)azo][1,1'-biphenyl]-4-yl]azo]2,7-naphthalenedisulfonic acid disodium salt;

7,7'-(carbonyldiimino)bis[4-hydroxy-3-(phenylazo)-2-naphthalenesulfonic acid disodium salt;

3-[[4-[[6-[(4-aminobenzoyl)amino]-1-hydroxy-3-sulfo-2-naphthalenyl]azo]-3,5-dimethylphenyl]azo]-1,5-naphthalenedisulfonic acid tri sodium salt;

5-[[4'-[(2-amino-8-hydroxy-6-sulfo-1-naphthalenyl)azo][1,1]-biphenyl]-4-yl]azo]-2-hydroxy-benzoic acid disodium salt;

3-[[4-(acetylamino)phenyl]azo]-4-hydroxy-7-[[[[5-hydroxy-6-(phenylazo)-7-sulfo-2 naphthalenyl]amino]carbonyl]amino]-2 naphthalenesulfonic acid disodium salt;

4-amino-5-hydroxy-6-[[4'-[(4-hydroxyphenyl)azo][1,1'-biphenyl]-4-yl]azo]-3-[(4-nithophenyl)azo]2,7-naphthalene disulfonic acid disodium salt;

4-amino-5-hydroxy-3-[[4'-[(4-hydroxy phenyl)azo][1,1'biphenyl]-4-yl]azo]-6-(phenylazo)-2,7-naphthalenedisulfonic acid disodium salt;

5-[[4'-[[8-amino-1-hydroxy-7-[(4-nitrophenyl)azo]-3,6-disulfo-2-naphthalenyl]azo[[1,1'-biphenyl]-4-yl]azo]-2-hydroxy-benzoic acid trisodium salt;

2,-]2-(4-nitro-2-sulophenyl)ethenyl]-5-[[4-[(4-sulfophenyl)azo]phenyl]-NNO-azoxy]-benzenesulfonic acid trisodium salt;

5,5'[carbonylbis[imino(2-sulfo-4,1-phenylene)azo][[bis[6-amino-V-hydroxy-2-naphthalenesulfonic]acid tetrasodium salt;

4,4'-[carbonylbis[imino(5-methoxy-2-methyl-4,1-phenylene)azo]]bis[5-hydroxy-2,7-naphthalenedisulfonic-acid]tetrasodium salt;

7-(benzoylamino)-4-hydroxy-3-[[4-[(4-sulfophenyl)azo]phenyl]azo]-2-naphthalenesulfonic acid disodium salt;

[-[[5,5'-[carbonylyl bis[imino(2-hydroxy-5 sulfo-4,1-phenylene)azo]]bis[6-hydroxy-2-naphthalenesulfonate]]ditetroammonium cuprate

[-[[7,7'-(carbonyldiimino)bis[4 hydroxy 3-[(2-hydroxy-5-sulfophenyl)azo]-2-naphthalenesulfonato](8-)]]dicuprate tetrasodium;

[-[[7,7'-iminobis[4-hydroxy-3-[[2-hydroxy-5-[(methylamino)sulfonyl]phenyl]azo]-2-naphthalenesulfonato]](6-)]]dicuprate disodium;

7-(benzoylamino)-4-hydroxy-3-[[2-methoxy-5-methyl-4-[(4-sulfophenyl)azo]phenyl]azo]-2-naphthalenesulfonic acid disodium salt;

5-[[4'[(26-diamino-3-methyl-5-sulfophenyl)azo]-3,3'-dimethyl[1,1'-biphenyl]-4-yl]azo]-2-hydroxy-benzoic acid disodium salt;

7,7'-iminobis[4-hydroxy-3-(phenylazo)-2-naphthalenesulfonic acid disodium salt;

3-3'-[3,3'-dimethyl[1,1'-biphenyl]-4,4'diyl)bis(azo)]bis[4-amino-5-hydroxy-1,-naphthalensulfonic acid disodium salt;

7,7'-iminobis[4-hydroxy-3-(phenylazo)-1-naphthelenesulfonic acid disodium salt;

5-[[4'-[2-amino-8-hydroxy-6-sulfo-1-naphthalenyl)azo][1,1'biphenyl]-4-yl]azo]-2-hydroxy-benzoic acid disodium salt;

5,5'[carbonylbis[imino(1-hydroxy-3-sulfo-6,2-naphthalenediyl)azo][bis-1 naphthalenesulfonic acid tetrasodium salt;

7,7'iminobis[4-hydroxy-3-(phenylazo)-2-naphthaolenesulfonic acid disodium salt;

3-[[4-(acetylamino)phenyl]azo]-4-hydroxy-7-[[[5-hydroxy-6-(phenylazo)-7-sulfo-2-naphthalenyl]amino]carbonyl]amino]-2-naphthalenesulfonic acid;

8-[[4'-[4-ethoxyphenyl)azo][1,1'-biphenyl]-4-yl]azo]-7-hydroxy-1,3-naphthalenedisulfonic acid disodium salt;

3-[[4-(acetylamino)phenyl]azo]-4-hydroxy-7-[[[[5-hydroxy-6-)phenylazo)-7-sulfo-2-naphthalenyl]amino]carbonyl]amino]-2-naphthalenesulfonic acid disodium salt;

5,5'[[1,1'biphenyl]-4,4'-diylbis(azo)]bis[6-amino-4-hydroxy-2-naphtholene sulfonic acid disodium salt;

7-amino-3-[[4'[(2-amino-8-hydroxy-6-sulfo-1-naphthalenyl)azo][1,1'-biphenyl]-4-yl]azo]-4-hydroxy-2-naphthalene sulfonic acid disodium salt;

5-[[4-[[1-hydroxy-6-(phenylamino)-3-sulfo-2-naphthalenyl]azo]-5-methoxy-2-methylphenyl]azo]-1-naphtholenesulfonic acid disodium salt.

The mineral carrier used to absorb the dye solution must be highly absorbant and must have a uniform particle size distribution. The particles making up the mineral carrier should have a diameter of less than 15 microns. In the preferred embodiment the average particle size of the indicator powder is greater than 1 micron and less than 10 microns. In a preferred embodiment of the invention, the mineral carrier will also have irregular shapes and be highly porous, thereby having a large surface area and the ability to absorb a substantial volume of liquid while remaining essentially dry. Diatomaceous earth, for example, will absorb up to two and one-half times its weight in liquid. The use of a high porosity, high surface area carrier promotes the even dispersion of the water soluble indicator dye throughout the mineral carrier thereby improving the sensitivity and effectiveness of the test method. The small concentration of dye used when compared to the large volume of mineral carrier provides a dried product having only a small amount of color which is apparent to the eye when the dry indicator powder is applied to a test surface thus providing the basis for an easily detectable color change if the indicator powder is wet by hydrocarbon fuel from a leak. The dye is also held on the surface of the mineral carrier because it is insoluble in the hydrocarbon fuel and therefore does not migrate from the mineral carrier to penetrate the painted surface being tested and cause a strain.

When conducting a test for fuel tank leaks in accordance with the method schematically represented in FIG. 2, a fuel tank 24, as shown in FIG. 3, is filled with a hydrocarbon base from storage tank 26 using a suitable pumping arrangement 27. The dye indicator powder is combined with a highly volatile organic solvent to form an indicator suspension 20. Referring to FIG. 3, the dye indicator powder may be stored in a suitable hopper 28 having a material feed conduit 29 and valving arrangement 30 for conveying the dye indicator powder from the hopper 28 to a container 31. A highly volatile organic solvent, contained in a tank 32, is combined with the dye indicator powder in container 31 by a second conduit 33 and valving arrangement 34 to form the indicator suspension 20. The indicator suspension is then applied to certain specified test surfaces at joints and around fasteners adjacent to fuel tanks to provide a thin film of dry powder on the test surface. This application is generally accomplished by spraying the indicator suspension using a standard venturi type spray apparatus, generally indicated at 35, and compressed air from source 36. The pressure of the compressed air should not exceed 45 psi because pressures in excess of 45 psi tend to cause surface damage to the painted test surface because of a sand blasting effect that results from the application of hard mineral particles to the soft painted surface under pressure. This problem is aggravated by the tendency of the organic solvent used in the suspension to dissolve or soften the surface of the paint thereby allowing suitably soluble dyes to migrate the painted surface.

As shown in FIG. 4, the spray apparatus 35 utilizes a constant source of compressed air as supplied by source 36 via a means for regulating the pressure of the compressed air or valve 37. A conduit 38 provides a means for supplying the pressure regulated compressed air to a venturi type valve 39 connected to a stray nozzle 40. Means for draining the suspension from the container 31 through the venturi valve 39 at a constant rate is provided by meter port 41 so that the volatile organic solvent evaporates and the indicator powder is propelled onto a test surface and uniformly distributed.

When applied the indicator powder is a light pink color if croceine dye is used. The color will turn to a bright red upon contact with fuel. The test does not require croceine dye or a pink to red color change in order to be successful. In order to successfully conduct the test, the dye chosen should be water or short chain alcohol soluble and when prepared as hereinbefore described should provide sufficient color contrast between the dry powder and fuel wet indicator to be easily discernable to the naked eye. Upon completion of the test the indicator powder is removed from the test surface by flushing the area with water, or by brushing, by means of, for example, a brush 42 as shown in FIG. 3, or by blowing the powder away with compressed air. As an alternative method of applying the indicator powder to the test surface, an aerosol spray could be used. This method would be particularly useful if the test were conducted under field conditions when large equipment and compressed air might not be available.

Generally, top coats used on the painted test surfaces are a metallic gray color which has been applied over a bright yellow primer. The dye used in the indicating powder should contrast well with these colors to faciliate ease in detecting leaks. Red, pink, violet and bright green dyes have been found to work well in this regard.

One advantage of using the test method and indicator powder disclosed and claimed herein arises from the insolubility of the dyes used in hydrocarbon fuels because water or other polar liquids will not give the color change and large color area representative of hydrocarbon fuel but will instead give only a small area of less intense color which will appear as a narrow advancing front moving away from the initial point of wetting.

Organic solvents which are acceptable for mixing the indicator suspension applied to the test surfaces are 1,1,1 trichloroethane, 1,1,2 trichloro-1,2,2 trifluorethane; 1,1,2 trichloroethane; trichloroethylene, sym-tetrachlorodifluroethane; sym-dischloroethylene; methylethyl ketone; 2-butanone, kexane, keptane, octane; 2-propanone; ethylacetate; cyclohexane, cyclohexene and mixtures thereof. Generally, the indicator suspension consists of from about 10 to about 30 volume percent of the indicator powder and from about 70 to about 90 volume percent of volatile organic solvent. Excellent results have been obtained with a 20 percent to 80 percent indicator-solvent mix ratio. If the indicator suspension is to be applied from an aerosol can it will also include a suspending agent such as aluminum stearate, magnesium stearate, calcium stearate or stearic acid. On occasion and depending on the solvent used, mixtures of suspending agents may be used as well as a mechanical mixing device contained within the aerosol container to facilitate an even application of indicator powder to the painted test surface.

While the invention has been particularly shown and described with reference to specific embodiment thereof, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. 

I claim:
 1. In a method for detecting leaks in a fuel tank which comprises introducing fuel into said fuel tank, allowing the fuel to soak said fuel tank for a period of time, applying an indicator to the surface being tested, observing color changes in said indicator and removing said indicator from the surface being tested; the improvement comprising:a. applying a substance suitable for detecting hydrocarbon fluid leaks by color change consisting essentially of a major portion of a dry inert mineral carrier and from about 0.1 to about 5.0 percent by weight of a direct dye soluble in water and low chain alcohols which is essentially non-staining on painted surfaces and which does not migratte into or penetrate painted surfaces, said painted surfaces containing a polyurethane or epoxy resin base; b. observing any changes in the color of the detecting substance; and c. removing the detecting substance from the surface being tested.
 2. The method of claim 1 wherein step (a) comprises:a. combining the substance suitable for detecting hydrocarbon fuel leaks with a volatile organic solvent to form an indicator suspension; and b. spraying said indicator suspension onto the surface being tested to form an even coating of said dry substance for detecting leaks on the surface being tested.
 3. The method of claim 2 wherein step (a) comprises combining from about 10 to about 30 percent by volume of the substance suitable for detecting leaks with from about 90 to about 70 percent by volume of said volatile organic solvent.
 4. The method of claim 3 wherein said volatile organic solvent is selected from a group consisting of 1,1,1 trichloroethane, 1,1,2 trichloro-1,2,2 trifluorethane, 1,1,2 trichloroethane, trichloroethylane, symtetrochlorodifluroethane, sym-dichlorethylene and mixtures thereof.
 5. The method of claim 3 wherein said volatile organic solvent is selected from a group consisting of methylethyl ketone, 2-butanone, kexane, heptane, octane, acetone, 2-propanone, ethylacetate, cyclohexane, cyclohexene and mixtures thereof.
 6. The method of claim 3 wherein said volatile solvent is substantially inert, has a toxicity tolerance limit over 200 ppm, is substantially insoluble in water and has a vapor pressure at 25° C. of from about 50 to about 300 mm of mercury.
 7. The method of claim 1 wherein step (c) comprises: providing a contant supply of water to a washing means and impinging a flow of water onto the surface being tested whereby the substance suitable for detecting leaks is flushed from said surface without damaging any coating thereon.
 8. An apparatus for detecting leaks in a fuel tank which comprises:a. means for combining an indicator powder consisting essentially of a major portion of a dry inert mineral carrier and from about 0.1 to about 5.0 weight percent of a direct dye soluble in water and lower chain alcohols with a volatile organic to form a suspension. b. means for introducing hydrocarbon base fuel into the tank being tested; c. means for applying said suspension to a painted test surface as a dry powder without staining or otherwise damaging said test surface; and d. means for removing said dry powder from the test surface upon completion of said test.
 9. The apparatus of claim 8 wherein said means for applying said suspension to a painted test surface further comprises:a. a constant source of compressed air; b. means for regulating the pressure of said compressed air within desired limits; c. means for supplying said pressure regulated compressed air to a venturi type valve; d. means for draining said suspension from a container through said venturi valve at a constant rate whereby the volatile organic solvent evaporates and the indicator powder is propelled onto said painted test surface and uniformly distributed thereon. 